INVESTIGADORES
DOCTOROVICH Fabio Ariel
artículos
Título:
Catalytic disproportionation of N-alkylhydroxylamines bound to pentacyanoferrates
Autor/es:
GUTIERREZ, M. M; ALLUISETTI, G; GAVIGLIO, C; DOCTOROVICH, F.; OLABE, J A; AMOREBIETA, V
Revista:
JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS
Editorial:
Royal Society of of Chemistry
Referencias:
Año: 2009 vol. 7 p. 1187 - 1194
ISSN:
0300-9246
Resumen:
The substituted hydroxylamines, CH3N(H)OH (N-methylhydroxylamine) and (CH3)2NOH (N,N-dimethylhydroxylamine), disproportionate catalytically to the corresponding alkylamines and oxidation products, only in the presence of [Fe(CN)5H2O]3-. Substitution kinetic measurements suggest an initial coordination step to Fe(II). Two parallel N- and O-coordination modes are considered with the subsequent formation of Fe(III), free aminyl (RNCH3) and nitroxide (RN(CH3)O) radicals (R = H, CH3). With CH3N(H)OH, bound nitrosomethane, CH3NO, has been characterized by UV-visible and IR spectroscopies. The mechanism is discussed on the basis of common and differential features with respect to the disproportionation of hydroxylamine catalyzed by the same Fe-fragment.
